Metal‐π Sites Localized Hydrogen‐*CO Coupling for Enhanced CO <sub>2</sub> Electromethanation
Abstract
ABSTRACT Electrochemical CO 2 ‐to‐CH 4 conversion on Cu–N–C single‐atom catalysts is fundamentally limited by *H/*CO spatial mismatch from numerous metal‐free CN matrix, where the long‐range hydrogen transfer easily causes *H coupling or *CO dimerization, ultimately impeding *CHO formation. Herein, we design a two‐dimensional metal–organic polymer catalyst featuring spatially adjacent Cu and 1H‐benzotriazole to form Cu‐π units, which achieves a Faradaic efficiency of 61% for CH 4 at 800 mA·cm −2 . Using Infrared free‐electron laser (IRFEL) nanospectroscopy, we identify the key Cu‐π coordination environment and low‐frequency bonding modes, unavailable by conventional IR techniques. Complementary in‐situ synchrotron radiation IR, electrochemical experiments and theoretical calculations reveal that π sites adsorb hydrated cations, enabling localized hydrogen supply to adjacent *CO on Cu sites and suppressing long‐range hydrogen transfer‐induced side reactions. This inorganic–organic synergy paves a new pathway to spatially match *H and *CO, advancing efficient CO 2 ‐to‐hydrocarbons conversion.
Article Details
Authors (17)
Mengyuan Liu
Tao Ding
Shuaiwei Jiang
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Yuanhua Sun
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Hui Huang
Center of Basic Molecular Science (CBMS), Department of Chemistry
Dong Liu
Hefei National Research Center for Physical Sciences at the Microscale, School of Chemistry and Materials Science, National Synchrotron Radiation Laboratory
Airong Xu
School of Nuclear Science and Technology Key Laboratory of Precision and Intelligent Chemistry Hefei National Research Center for Physical Sciences at the Microscale National Synchrotron Radiation Laboratory University of Science and Technology of China Hefei P.R. China
Lanyue Zhang
Xiaokang Liu
State Key Laboratory of Geomicrobiology and Environmental Changes, School of Earth Sciences, China University of Geosciences
Huijuan Wang
Tong Liu
Jiayu Dai
College of Science, National University of Defense Technology 1 , Changsha 410073,
Chengyuan Liu
National Synchrotron Radiation Laboratory
Yang Pan
National Synchrotron Radiation Laboratory
Jiawei Xue
National Synchrotron Radiation Laboratory
Jun Bao
SINOPEC Research Institute of Petroleum Processing
Tao Yao
National Synchrotron Radiation Laboratory, State Key Laboratory of Precision and Intelligent Chemistry, School of Nuclear Science and Technology